Asymmetric Amination Catalyzed by Dirhodium(II) Complexes

• Project/Area Number: 19790001
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Chemical pharmacy
• Research Institution: Hokkaido University
• Principal Investigator: ANADA Masahiro Hokkaido University, 大学院・薬学研究院, 助教 (90344473)
• Project Period (FY): 2007 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥3,690,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥390,000); Fiscal Year 2008: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2007: ¥2,000,000 (Direct Cost: ¥2,000,000)
• Keywords: 合成化学 / 不斉触媒反応 / ロジウム(II)錯体 / イミノヨーディナン / ナイトレン / α-アミノケトン / ベンゾモルファン化合物 / α-フェニルグリシン誘導体 / アジリジン

Research Abstract

ロジウム(II) 錯体触媒を用いた、スルホニルイミノヨージナンをナイトレン前駆体とする鎖状ケトン由来のシリルエノールエーテルの不斉アミノ化反応ついて検討を行った。その結果、NsN=IPh (Ns = 2-NO2C6H4SO2)をナイトレン前駆体、Rh2(S-TFPTTL)4 を触媒に用いると最高95%の不斉収率でα-アミノケトンが得られることを見出し、本法を機軸とする(.)-リトドリン、(.)-メタゾシンの触媒的不斉合成を達成した。また、ベンゼン溶媒中Rh2(S-TCPTTL)4を触媒に用いフェニル酢酸由来のシリルケテンアセタールの不斉アミノ化反応を行うとフェニルグリシン誘導体が最高不斉収率99%で得られることが判明した。さらに、シクロヘキサノン由来のシリルエノールエーテルを基質とした場合にはアリル位C.H結合へのナイトレンの挿入反応が位置およびエナンチオ選択的に進行することを見出し、本法を鍵工程とするヒガンバナアルカロイド(.)-パンクラシンの形式不斉合成を達成した。

Research Products

• [Journal Article] Asymmetric Formal Synthesis of (-)-Pancracine via Catalytic Enantioselective C-HAmination Process (2009)
  • Author(s): Anada, M, Tanaka, M, Shimada, N, Nambu, H, Yamawaki, M, Hashimoto, S
  • Journal Title: Tetrahedron 65 Pages: 3069-3077
  • Peer Reviewed
• [Journal Article] Asymmetric Formal Synthesis of (-)-Pancracine via Catalytic Enantioselective C-H Amination Process (2009)
  • Author(s): M. Anada et.al.
  • Journal Title: Tetrahedron 65 Pages: 3069-3077
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Synthesis of (-)-Ritodrine Hydrochloride via Silyl Enol Ether Amination Using Dirhodium(II) Tetrakis[tetrafluorophthaloyl-(S)-tert-leucinate] (2008)
  • Author(s): Tanaka, M, Nakamura, S, Anada, M, Hashimoto, S
  • Journal Title: Heterocycles 76 Pages: 1633-1645
  • Peer Reviewed
• [Journal Article] Catalytic Enantioselective Intermolecular Cycloaddition of 2-Diazo-3,6-diketo -ester-Derived Carbonyl Ylides with Alkynes and Styrenes Using Chiral Dirhodium(II) Carboxylates (2008)
  • Author(s): Shimada, N, Anada, M, Nakamura, S, Nambu, H, Tsutsui, H, Hashimoto, S
  • Journal Title: Org. Lett 10 Pages: 3603-3606
  • Peer Reviewed
• [Journal Article] Catalytic Enantioselective Intermolecular Cycloaddition of 2-Diazo-3, 6-diketoester-Derived Carbonyl Ylides with Alkynes and Styrenes Using Chiral Dirhodium(II) Carboxylates (2008)
  • Author(s): N. Shimada et.al.
  • Journal Title: Organic Letters 10 Pages: 3603-3606
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Synthesis of (-)-Ritodrine Hydrochloride via Silyl Enol Ether Amination Using Dirhodium(II) Tetrakis[tetrafluorophthaloy1-(S)-tert-leucinate] (2008)
  • Author(s): M. Tanaka et.al.
  • Journal Title: Heterocycles 76 Pages: 1633-1645
  • Peer Reviewed
• [Journal Article] Catalytic Asymmetric Hetero-Diels-Alder Route to a Key Intermediate for the Synthesis of Calyxin L (2007)
  • Author(s): Washio, T, Nambu, H, Anada, M, Hashimoto, S
  • Journal Title: Tetrahedron: Asymmetry 18 Pages: 2606-2612
  • NAID: 120000950252
  • Peer Reviewed
• [Journal Article] Enantioselective Amination of Silylketene Acetals with (N-Arylsulfonylimino)phenyliodinanes Catalyzed by Chiral Dirhodium(II) Carboxylates: Asymmetric Synthesis of Phenylglycine Derivatives (2007)
  • Author(s): Tanaka, M, Kurosaki, Y, Washio, T, Anada, M, Hashimoto, S
  • Journal Title: Tetrahedron Lett 48 Pages: 8799-8802
  • NAID: 120000950257
  • Peer Reviewed
• [Journal Article] Catalytic Enantioselective Amination of Silyl Enol Ethers Using Chiral Dirhodium(II) Carboxylates: Asymmetric Formal Synthesis of (-)-Metazocine (2007)
  • Author(s): Anada, M, Tanaka, M, Washio, T, Yamawaki, M, Abe, T, Hashimoto, S
  • Journal Title: Org. Lett 9 Pages: 4559-4562
  • Peer Reviewed
• [Journal Article] Asymmetric Syntheses of Diarylheptanoid Natural Products, (-)-Centrolobine and (-)-de-O-Methylcentrolobine via Hetero-Diels-Alder Reaction Catalyzed by Dirhodium(II) Tetrakis[(R)-3-(benzene -fused-phthalimido)-2-piperidinonate] (2007)
  • Author(s): Washio, T, Yamaguchi, R, Abe, T, Nambu, H, Anada, M, Hashimoto, S
  • Journal Title: Tetrahedron 63 Pages: 12037-12046
  • Peer Reviewed
• [Journal Article] Catalytic Enantioselective Aziridination of Alkenes Using Chiral Dirhodium(II) Carboxylate (2007)
  • Author(s): Yamawaki, M, Tanaka, M, Abe, T, Anada, M, Hashimoto, S
  • Journal Title: Heterocycles 72 Pages: 709-721
  • Peer Reviewed
• [Journal Article] Catalytic Enantioselective Tandem Carbonyl Ylide Formation/1,3-Dipolar Cycloaddition Reactions of α-Diazo Ketones with Aromatic Aldehydes Using Dirhodium(II) Tetrakis[N-benzene-fused-phthaloyl(S)-valinate] (2007)
  • Author(s): Tsutsui, H, Shimada, N, Abe, T, Anada, M, Nakajima, M, Nakamura, S, Nambu, H, Hashimoto, S
  • Journal Title: Adv. Synth. Catal 349 Pages: 521-526
  • Peer Reviewed
• [Journal Article] Catalytic Enantioselective Aziridimation of Alkeness Using Chiral Dirhodium(II) Carboxylates (2007)
  • Author(s): M. Yamawaki et al.
  • Journal Title: Heterocycles 72 Pages: 709-721
  • Peer Reviewed
• [Journal Article] Catalytic Enantioselective Amination of Silyl Enol Ethers Using Chiral Dirhodium(II) Carboxylates : Asymmetric Formal Synthesis of (-)-Metazocine (2007)
  • Author(s): M. Anada et al.
  • Journal Title: Organic Letters 9 Pages: 4559-4562
  • Peer Reviewed
• [Journal Article] Enantioselective Amination of Silylketene Acetals with (N-Arylsulfonylimino)Phenyliodimanes Catalyzed by Chiral Dirhodium(II) Carboxylates : Asymmetric Synthesis of Phenylglycine Derivatives (2007)
  • Author(s): M. Tanaka et al.
  • Journal Title: Tetrahedron Letters 48 Pages: 8799-8802
  • Peer Reviewed
• [Journal Article] Enantioselective Construction of 2,8-Dioxabicyclo[3.2.1]octane Ring System via [2,3]-Sigmatropic Rearrangement of Oxonium Ylide Using Chiral Dirhodium (II) Carboxylates
  • Author(s): Shimada, N., Nakamura, S., Anada, M., Shiro, M, Hashimoto, S
  • Journal Title: Chem. Lett (in press)
  • NAID: 10025122221
  • Peer Reviewed
• [Presentation] A Dirhodium(II) Carboxamidate Complex as a Chiral Lewis Acid Catalyst for Enantioselective Hetero-Diels-Alder Reactions (2008)
  • Author(s): Anada, M, Washio, T, Watanabe, Y, Shimada, N, Hashimoto, S
  • Organizer: 3rd International Symposium on Cutting-Edge Organic Chemistry in Asia
  • Place of Presentation: Hangzhou, China
  • Year and Date: 2008-10-20
• [Presentation] Enantioselective Amination Reactions Catalyzed by Dirhodium(II) Carboxylates (2008)
  • Author(s): Tanaka, M, Kurosaki, Y, Washio, T, Anada, M, Hashimoto, S
  • Organizer: 17th International Conference on Organic Synthesis
  • Place of Presentation: Daejeon, Korea
  • Year and Date: 2008-06-26
• [Presentation] Dirhodium(II)-Catalyzed Enantioselective Hetero-Diels-Alder Reaction: Catalytic, Enantioselective Synthesis of Cyclic Diarylheptanoid Natural Products (2008)
  • Author(s): Washio, T, Anada, M, Hashimoto, S
  • Organizer: 17th International Conference on Organic Synthesis
  • Place of Presentation: Daejeon, Korea
  • Year and Date: 2008-06-26
• [Presentation] ロジウム(II)アミダート錯体触媒を用いた不斉ヘテロDiels-Alder 反応 (2008)
  • Author(s): 穴田仁洋
  • Organizer: 日本薬学会北海道支部第130回例会総説講演
  • Place of Presentation: 札幌
  • Year and Date: 2008-05-10
• [Presentation] ロジウム(II)カルボキシラート錯体を用いる触媒的不斉アミノ化反 (2007)
  • Author(s): 穴田仁洋
  • Organizer: 若手研究者のための有機化学札幌セミナー
  • Place of Presentation: 札幌
  • Year and Date: 2007-10-05
• [Presentation] Rh(II)-Catalyzed Enantioselective Hetero-Diels-Alder Reaction: Enantioselective Synthesis of Cyclic Diarylheptanoid Natural Products (2007)
  • Author(s): Washio, T, Anada, M, Hashimoto, S
  • Organizer: 14th IUPAC Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS14)
  • Place of Presentation: 奈良
  • Year and Date: 2007-08-02
• [Presentation] Dirhodium(II)-Catalyzed Enantioselective Hetero-Diels-Alder Reaction (2007)
  • Author(s): Anada, M, Washio, T, Watanabe, Y, Shimada, N, Hashimoto, S
  • Organizer: 第1回プロセス化学国際シンポジウム(ISPC08)
  • Place of Presentation: 京都
  • Year and Date: 2007-07-29
• [Presentation] A Dirhodium(II) Carboxamidate Complex as a Chiral Lewis Acid Catalyst for Enantioselective Hetero-Diels-Alder Reaction" 特定領域研究「炭素資源の高度分子変換」 (2007)
  • Author(s): Washio, T, Anada, M, Hashimoto. S
  • Organizer: キラル有機分子触媒の国際シンポジウム
  • Place of Presentation: 大津
  • Year and Date: 2007-05-28
• [Presentation] Enantioselective Aminations Catalyzed by Dirhodium(II) Carboxylates (2007)
  • Author(s): Anada, M, Tanaka, M, Yamawaki, M, Hashimoto, S
  • Organizer: PSWC2007
  • Place of Presentation: Amsterdam, Netherlands
  • Year and Date: 2007-04-23
• [Patent(Industrial Property Rights)] 固相担持型金属錯体触媒 (2008)
  • Inventor(s): 橋本俊一, 穴田仁洋
  • Industrial Property Rights Holder: 北海道大学
  • Filing Date: 2008-01-31
• [Patent(Industrial Property Rights)] α-アミノケトンの製法 (2007)
  • Inventor(s): 橋本俊一, 穴田仁洋
  • Industrial Property Rights Holder: 科学技術振興機構
  • Patent Publication Number: 2007-204442
  • Filing Date: 2007-08-16
• [Patent(Industrial Property Rights)] 不斉触媒 (2007)
  • Inventor(s): 橋本俊一, 穴田仁洋
  • Industrial Property Rights Holder: 北海道大学
  • Patent Publication Number: 2007-203269
  • Filing Date: 2007-08-16